Coated sheet material



sept.15,1936. AABRAMSHAL l 42,054,112.

v4COATED SHEET MATERIAL' Filed oct. 1e, 1953 @E @4L/@m5 Patented Sept. 1 5, 1.936

COATED SHEET MATERIAL Allen Abrams and Charley L. Wagner, Wausau,

Wis., assignors to Marathon Paper Mills Company, Rothschild, Wis., a corporation of Wilconsin appuesunn october 1s, 193s. serial Nit-s931141 1o claim.,l (ci. :i1-ss) i This invention relates to a coated sheet material or to laminated material and to a method of producing the same.

It has heretofore been suggested. in connection with the impregnation of fabric and leather materials, to use mixtures of various substances, including rubber, with paraffin or other waxy materials. In general, the objective has been to secure a solution of rubber or related materials in a wax that will have a relatively low viscosity and therefore good penetrating properties. For this purpose, it has been suggested to use volatile solvents or thinners, and also, where Volatile solvents are omitted, to heat the 'solution to a sufiiciently high temperature or otherwise treat the solution so as to greatly lower its viscosity.

For our purposes, however, we have found it necessary to employ a solution of rubber orrubber-like substance in wax in such proportions as to have a relatively high viscosity. The solution for coating or adhesive purposes should be one that does not strike through the paper or other web or sheet material to which it is applied, but should remain primarily as a surface coating. Such coating should be tough, iexible and thermoplastic and/or adhesive,l and should lrnpart moistureproofness, waterproofness and gasproofness to the paper'or other base.v V

It is therefore an object -of the present invention to provide a sheet coated with a lm material that is tough, flexible and thermoplastic and/or adhesive, and that possesses a relatively high degree of moistureproofness, waterproofness and gasproofness.

It is a further important object of this invention to provide a laminated sheet or web materialhaving an adhesive layer joining the superimposed laminations that imparts moisturev proofness, waterproofness and. gasproofness to the laminated article and that is substantially colorless and odorless. It is a further object of the present inventio to provide a flexible, heat-sealing sheet material having a waterproof, non-tacky surface coating comprising rubber and paraffin wax.

It is a further object of this invention to provvide a coated sheet material having heat-sealing qualities capableof effecting a strong bond between board,'paper, metal'foil and the like, with- `out striking through or impregnating the component laminations.

It is an additional object of this invention to provide a process for producing flexible, moistureproof, waterproof andgasproof sheet'material having heat-sealing properties.

Other and further objects of this inventionlwill be evident from the following specification and the accompanying drawing.

On the drawing:

Figure 1 represents a diagrammatic side elevation of a coating machine for producing our coated sheet material.

Figure 2 represents a diagrammatic side elevational view of a machine for 'producing our laminated sheet material, with the paper webs in section and exaggerated in thickness for clarity.

The composition which we use for coating and laminating purposes comprises a solution of rubber or a rubber-like substance ina wax or waxdike substance. Among the suitable rubber and spermaceti.

Since solutions of rubber in wax have widely varying viscosities, depending uponjthe proportions and particular ingredients' used and upon the conditions of preparation, we have found it is of assistance iirst to determine the limits of viscosity within which the solutions show satisfactory results. In general, a solution to be suitable for coating and laminating purposes should have a viscosity of not less than about 8000 secs. (measured onY a Scott viscosimeter at CJ.

. Below this viscosity, there is a tendency of the solution to strike through or penetratev the sheet coated therewith.

The ability of a solution to strike through, however, is naturally different with different weights and kinds'of paper. The less hydrated and thinner papers require a solution of greater viscosity to prevent penetration, whereas solui tions of lower viscosities can be employed with heavier and more highly hydrated papers. Consequently, the viscosity of the rubber-wax solu-l tionv may be as low as 1000 to 2000 secs. when the solution is to be used with heavier and/or 'more highly hydrated paper or with 'other sheet material having greater impenetrability toward the coating solution. It is, of course, possible to wax a paper on one side only with straight paraffin wax without having the wax strike into'l varied through even wider ranges than above indicated, although vviscosities above 8000 secs. ap-

canized rubber in melted paraiiin wax. The par-l amn wax is heated to a temperature of 180 to 220 F. and the rubber is added in a shredded,

or other subdivided condition. The temperaturedropsupon the addition of the rubber and should preferbaly be maintained at between 160 and 180 F. andthe mixture stirred until the rubber is completely dissolved. It is necessary to keep `the temperature of the rubber-parailin mix at about the temperatures indicated in order to avoid overheating, which results in an undesirable darkening ot the mass and imparts considerable -odor to it. In addition, overheating reduces the viscosity ,of the solution considerably.

After the rubber has beenl in the paraffin for about an hour, the pieces of rubber are sumcient- 1y softened `and swollen to permit complete disintegration by agitation. With an ordinary revolving blade stirrer, it requires 5 to 6 hours to produce a smooth solution of the rubber and paraiiin, but with equipment specially designed for this work, the time can be materially reduced.

In compositions of our invention up to about 30% by weight of the mixture of pale crepe-rubber, at which point the viscosity becomes too' great for ready application, the cohesiveness of the mixture and its adhesiveness,'as a coating, increase with the viscosity of the mixture. It is therefore important not to lower the viscosity of any given mixture unnecessarily, as by increasing the temperature or timeof heating of the ingredients when dissolving the rubber in the wax. The viscosity, for a given concentration of rubber in wax, decreases with the time of heating.

As to the eiectloi temperature on viscosity, we

- havel found that with a given concentration of the viscomty decreases with the time of'millingl pale crepe rubber in wax, the viscosity at a given temperature is inversely proportional to the tem'- perature to which the mixture has been heated during or after the solution period. For instance, the eil'ect of temperature on the viscosity of a solution of 6% pale crepe rubber in parailin wax was determinedby quickly heating the mixturel to a given temperature and holding at that temperature for one hour, with thel following results:

With a given concentration of rubber in wax,

the rubber used in the mixture.

With'a given concentration of rubber in wax, very small percentages of a rubber accelerator.

such as .mercaptobenzothiazoL will markedly reduce the viscosity. This efiect is dependent on the particular accelerator used and also upon the percentage added.

With a given concentration of rubber in wax, vulcanizing agents (such reduce the viscosity.

With a given concentration of rubber in wax, the addition of anti-oxidants, such as symmetas sulphur chloride)v v of. the doctor bar.

little or no eiect on the viscosity. y

Additional viscosity may be obtained over that of pure paraiiin by the addition to paraflln of other 'materials such aslaluxlninum stearate, but the resultant mixture does not have as good adhesiveness nor `moistureprooiness as a rubberrical dibetaenaphthyl-p-phenylene diamine, have paraiiln mixture of equal viscosity.

When the percentage of rubber isvtoo low, the composition is not suiiiciently flexible at low temperatures for use as a coating and does not have satisfactory adhesive properties. co'sity isl so low that the composition strikes through the sheet material. When too much rubber is used, the composition is too Viscous and ,is too tough to be a satisfactory adhesive.

For this reason we prefer, when using unvulcanized rubber, to keep the percentage of rubber in our composition betweenv l0 and 20%, although some of the advantages of -our invention can be obtained with the rubber as low as 6% v or as high as 30%, by weight, of the mixture.

In the case of gutta percha, thepercentage of gutta percha may be increased above 30% without causing too high a viscosity. In general,

higher percentages .of milled rubber and gutta percha are required to give viscosities corresponding with those obtained by the use of un- 'vulcanized, unmilled rubber.

Pale crepe rubber or smoked sheets, may be used most satisfactorily. but pale crepe rubber ispref e erable because of the odor and color of the smoked sheet. A preferred formula for our composition is as follows:

Percent by weight Paraiiin wax (M. P. 120-140 F.) r 88 Rubber (Pale crepe) '12 Resinous materials may be added to our composition, with a slight advantage in sealing properties but with a greater tendency to block. By the term block is meant the property possessed by sheet material whenstacked to adhere together, as for. instance under unusually high climatic temperature. The use of gumA rosin, for example, to replace an equal weight, up to about 15% of the paratlin can be eiectedwithout seriously increasing the blocking tendency of our composition. When the sheets are piled together they do not under ordinary conditions stick to each other or block, but to further prevent blocking, the surfaces may be dusted with substances, such as mica.

Referring to the drawing, in Fig. lthe reference numeral 3 designates a web vof brous material which is to be coated by our process. The

Also, the vis-Y sheet 3 passes over a roller 5 which is heated by.

steam entering through the pipe E, or by other v suitable means. While this roll may be rotatably mounted, if desired, we prefer to provide a stationary mounting and permit the sheet material to termining the thickness of the coating on the fin,-

ished sheet material. Coating material 8 such as previously described is supplied to the web ahead As the web passes underneath the coating material, it acquires a thin film of said material, the thickness of which is made uniform by the doctor bar 1. No container for the coating material is ordinarily required, since it is sumciently viscous to remain in the position shown,

The doctor `bar 1 may be maintained at a constant temperature by a heating element Il which is supplied with electric current by the conductors I2. Other suitable heating means may also be employed. A

After passing under the doctor bar 1, the web \material passes over rolls I5 and IB which are cooled by water entering through pipes I1 or Il or by other suitable means.

Our invention also contemplates other methods of coating wherein either one or both sides of a 4be coated.

The temperature to which the roll l and the doctor 1 are heated may vary between 180 and 230 F. In any case, the temperature must be suflicient to soften the composition used and cause it to adhere to the paper during the coating process. l

The thickness of the layer of composition on Aweb of material, such as fiber or paper board may our paper may be varied by adjusting the distance between the roll li and the doctor 1. We prefer to adjust our device so that between 10 and 20 pounds of our composition will be coated onto each ream of paper (3,000 square feet) but any amount between 4 and 50 pounds per ream will produce coatings that are satisfactory for certain purposes,

Our new paper product is not only waterand d moistureproof but it has the important advantage of being heat-sealing. 1f Aa piece of paper coatedA on one side in accord with our process is placed upon another untreated paper and the two sheets are simultaneously heated and pressed together, they will adhere ilrmly over their entire contacting surfaces.. We nd that the minimum temperature and time required to make a suitable heat seal will vary slightly with the composition oi the mixture of rubber and paramn. If it contains, for example 12% of pale` crepe rubber, it

,will seal in not over 3 seconds at a temperature of 300 to 500 F., dependent upon the thickness of the paper towhich the seal is being made. We have found that satisfactory seals may be made at temperatures ranging from 200 to 500 F.

An important diiIerence between this and prior coatings of this type is that the coating material of our preferred composition does not soak into the paper but remainsl as a surface layer. There is no objectionable striking through of the coating'to give a discoloration on the exposed or opposite surfaces of acoated or laminated sheet.

Our newI coating compositionhas other important advantages over previously-known materials of this `type. i The composition coating is non-tacky and much more elastic and flexible than pure paramn wax coatings, especially at low temperatures. ity are much less a'ected by cold than is paraffin wax itself. Consequently, the coated paper of our invention is much less liable to lose moistureproofness on wrinkling than is a corresponding paper treated with parafn wax alone. The coating composition itself is substantially colorless,

tasteless and odorless and moisture-, waterand odor.

In fact, its elasticity and flexibily In Fig. 2 there is illustrated diagrammatically a method of forming laminated sheet or web material. The apparatus forv carrying out this method includes a pair of heated squeeze rolls 2| and 22, arranged in either vertical or horizontal alignment, which may be suitably heated by steam introduced throughpipes 24 and 25. The rolls 2-I and 22 are provided with means (not shown) for adjusting the pressure exerted by one roll against the other. Other rolls, 21 and 28 may be 4 suitably used as chillrolls, although these may be dispensed with entirely or the number varied.

Webs 2l, 26 of the material to' be laminated' are led over the respective rolls 2i and 22 to pass between the nipof these rolls and thence between rolls 21 and 28. A mass of coating material 28 is positioned in' advance of the nip between the rolls 2l 'and 22 and is picked up by thd surfaces of the web material26 as the webs pass into the nip of the rolls. The rolls 2l and 22 are carr-ied ata sufllciently high temperature to soften the viscous mass of coating material and to permit it to be"spread out uniformly over the surfaces of the webs 26. The temperature of the viscous mass may satisfactorily be about 220 F. The thickness of the sealing layer is governed by 4the pressure exerted against the composite web by the rolls 2| and 22.

Laminated sheet material made with the adhesive composition above described has the advantage of being moistureproof, waterproof and gasproof to a high degree. At the sam'e time. white laminations may be produced. This is a distinct advantage, since the present asphalt laminated sheets are dark colored and have an The strength of the adhesive seal uniting the laminations is such that the component laminations can rarely be separated, when the preferred adhesive composition is used, without rupturing the material of the laminations themselves. We also secure a printabley and gluable product. Where lightweight translucent papers v. are used, such as bleached sulphite, greaseprcof, glassine and parchment papers and the like, very and the like, and we contemplate its use in connection with each of these substances.

liurther,` where it is desired to provide a white Ior colored coated sheet, we have found that suitable white or colored pigments may be incorporated into the coating composition. This is best accomplished by incorporating the pigments into the rubber in the rst instance and then dissolv` ing the pigmented rubber in the paraffin wax in the manner already described. By ourvmethod, a permanent suspension of the pigments in the parailin wax-rubber solution is obtained.

The term rubber as' used in the appended claims is intended to include the use of india rubber or Hevea rubber. gutta rubber, and their natural or synthetic` equivalents for the purpose of this invention, singly or mixtures thereof. It is understood of course that in the coated product the rubber content may be vulcanized orvunvulcanized as desired,

The term "wax" as used in the -appended claims is intended to include the use of paramn wax. beeswax, spermaceti, vcandelilla, carnauba and their natural or synthetic equivalents, singly or.

' 1. The method of coating papenandthe like.. .which comprises passing a web of paper. overa heated surface into contactwith a mass resting on said/web of a heated plastic composition of rubber and paraflin wax having a viscosity of at least 8000 secs. (Scott viscosimeter at 90 C.)

and controlling the thickness of the coating of said composition that adheres to said-web by means of a rigid heated edge closely spaced from said first heated surface.

2. The method of coating web material, which comprises drawing said web material between an arcuate heated surface and a heated rigid straight edge closely spaced from said surface, supplying a coating composition to saidl web from a heated, plastic mass of the composition resting on saidV web ahead of said straight edge. said composition comprising a mixture of from 6 to 30% rubber and from 94 to 70%,paraiiin wax. and adjusting said straight edge to control the thickness of said coating. a

3. 'Ihe method of coating web material, which comprises drawing said web material over a heated curved supporting surface. applying directly to said web while so supported a heated plastic mass of a rubberwax composition of such high viscosity as to be self-retaining of its unitary mass without confining walls and smoothing ci! the plastic composition n.dhering to said web to obtain a uniform smooth coating on said web.

4. The method of preparing heat-sealing sheet material having a flexible, moistureproof, waterproof and gasproof surface coating, which comprises forming a composition of paraihn wax and unvulcanized rubber containing-'from 6 to 30% of rubber and from 94 to 70% of wax, depositing a heated mass of said composition having a viscosity of at least 8000 secs. (Scott visu cosimeter at 90 C.) upon a supported traveling DISCLAIMEB- L. Wagner: Wausau; Cos` Patent dated September -15 1935 TED HEET 2,054,11 3.-Allen Abrams and Charley MATERIAL.

web, heating said web while in direct contact with said mass to cause said composition to adhere to said web. applying heat directly to-the upper surface of thev composition adhering to said web and leveling oil' said adhering composition to obtain a uniform smooth coating on said web.

5. Paper and the like having a superiicially adherent thin flexible non-tacky moisture-waterand gas-proof rubber-wax composition, said layer being formed from a composition compris' ing from 9 4 to 70% parailln and from 6 to 30% pale crepe rubber and having a viscosity of atleast 8,000 secs. (Scott lviscosimeter at 90. C.)

8. A iibrous sheet material having a supernadherent thin exible non-tackymoisturewate-and gas-proof layer of rubber-wax composition formed from a composition comprising waxl and a suiiicient quantity of rubber so compounded as to have aviscoslty above l8.000 secs. (Scott viscosimeter at 90 C.) j 5 7, The method of coatingpaper and the like which comprises a web 0I .over a heated surface into contact with a mass-` resting on said web of va heated plastic composition coin-l prising -rubber and parailln wax ayiscosity of at least 8,000 secs. (Scott viscosimeter at 90 C.) and controlling the thickness of the coating of said composition that adheres to said web .by adjustable heated meansxclosely spaced fromsaidrstheatedsurface. l

8." The method jof coatingweb material, which 'comprises drawing said web material over a heated supporting surface, applying directly 'to said web whileso supported a heated plastic mass of a rubber-wax composition of such high viscosity as to be self-retainingof .its unitary mass without confining walls and smoothing oi! the plastic composition adhering to said web to obtain a uniform smooth coating on said web.

9. The method of supercially coating sheet- `ing material with yan elastic ilexible non-tacky moisture-waterand gas-proof layer which comprises applying thereto a plastic rubber-wax composition to form a coating of suitable thickness,

and cooling the coated sheet to solidify saidcoating composition.

1o. A sheet material having a supernciauy-ad-vherent thin flexible non-tacky moisture-waterand gasproof layer of rubber-wax composition formed from a composition comprising wax and a sumclent quantity of rubber so compounded as to have a viscosity above 8,000 secs. (Scott viscosimeter at CJ.

Disclaimer led February -7, 14988, by the assignee, Marathon Paper Mills ompa'rty. Hereby d1scla1ms from the scope of claim 5 of said patent any product except wherein the supercially adherent layer of rubber-Wax composition is f compositlon comprislng Wax and rubber while hot I rmed from the and wherein theviscosity as set forth in said claim is a property of said com osition of wax and i rub compounded and as used 1n auch forming procless; l Y ber ais uut-muy And hereby disclaims from their natural or synthetic equivalents, singly or.

mixtures thereof, suitable for the purpose of this invention.

We are aware that numerous details of our invention may be varied through a wide range without departing from the principles thereof, and we, therefore, do notv purpose limiting the patent granted hereon otherwise than necessitated by the prior art.

We claim as our invention:v I

' 1. The method of coating papenandthe like.. .which comprises passing a web of paper. overa heated surface into contactwith a mass resting on said/web of a heated plastic composition of rubber and paraflin wax having a viscosity of at least 8000 secs. (Scott viscosimeter at 90 C.)

and controlling the thickness of the coating of said composition that adheres to said-web by means of a rigid heated edge closely spaced from said first heated surface.

2. The method of coating web material, which comprises drawing said web material between an arcuate heated surface and a heated rigid straight edge closely spaced from said surface, supplying a coating composition to saidl web from a heated, plastic mass of the composition resting on saidV web ahead of said straight edge. said composition comprising a mixture of from 6 to 30% rubber and from 94 to 70%,paraiiin wax. and adjusting said straight edge to control the thickness of said coating. a

3. 'Ihe method of coating web material, which comprises drawing said web material over a heated curved supporting surface. applying directly to said web while so supported a heated plastic mass of a rubberwax composition of such high viscosity as to be self-retaining of its unitary mass without confining walls and smoothing ci! the plastic composition n.dhering to said web to obtain a uniform smooth coating on said web.

4. The method of preparing heat-sealing sheet material having a flexible, moistureproof, waterproof and gasproof surface coating, which comprises forming a composition of paraihn wax and unvulcanized rubber containing-'from 6 to 30% of rubber and from 94 to 70% of wax, depositing a heated mass of said composition having a viscosity of at least 8000 secs. (Scott visu cosimeter at 90 C.) upon a supported traveling DISCLAIMEB- L. Wagner: Wausau; Cos` Patent dated September -15 1935 TED HEET 2,054,11 3.-Allen Abrams and Charley MATERIAL.

web, heating said web while in direct contact with said mass to cause said composition to adhere to said web. applying heat directly to-the upper surface of thev composition adhering to said web and leveling oil' said adhering composition to obtain a uniform smooth coating on said web.

5. Paper and the like having a superiicially adherent thin flexible non-tacky moisture-waterand gas-proof rubber-wax composition, said layer being formed from a composition compris' ing from 9 4 to 70% parailln and from 6 to 30% pale crepe rubber and having a viscosity of atleast 8,000 secs. (Scott lviscosimeter at 90. C.)

8. A iibrous sheet material having a supernadherent thin exible non-tackymoisturewate-and gas-proof layer of rubber-wax composition formed from a composition comprising waxl and a suiiicient quantity of rubber so compounded as to have aviscoslty above l8.000 secs. (Scott viscosimeter at 90 C.) j 5 7, The method of coatingpaper and the like which comprises a web 0I .over a heated surface into contact with a mass-` resting on said web of va heated plastic composition coin-l prising -rubber and parailln wax ayiscosity of at least 8,000 secs. (Scott viscosimeter at 90 C.) and controlling the thickness of the coating of said composition that adheres to said web .by adjustable heated meansxclosely spaced fromsaidrstheatedsurface. l

8." The method jof coatingweb material, which 'comprises drawing said web material over a heated supporting surface, applying directly 'to said web whileso supported a heated plastic mass of a rubber-wax composition of such high viscosity as to be self-retainingof .its unitary mass without confining walls and smoothing oi! the plastic composition adhering to said web to obtain a uniform smooth coating on said web.

9. The method of supercially coating sheet- `ing material with yan elastic ilexible non-tacky moisture-waterand gas-proof layer which comprises applying thereto a plastic rubber-wax composition to form a coating of suitable thickness,

and cooling the coated sheet to solidify saidcoating composition.

1o. A sheet material having a supernciauy-ad-vherent thin flexible non-tacky moisture-waterand gasproof layer of rubber-wax composition formed from a composition comprising wax and a sumclent quantity of rubber so compounded as to have a viscosity above 8,000 secs. (Scott viscosimeter at CJ.

Disclaimer led February -7, 14988, by the assignee, Marathon Paper Mills ompa'rty. Hereby d1scla1ms from the scope of claim 5 of said patent any product except wherein the supercially adherent layer of rubber-Wax composition is f compositlon comprislng Wax and rubber while hot I rmed from the and wherein theviscosity as set forth in said claim is a property of said com osition of wax and i rub compounded and as used 1n auch forming procless; l Y ber ais uut-muy And hereby disclaims from 

